WO2014196768A1 - Résine polyester biodégradable et article la contenant - Google Patents

Résine polyester biodégradable et article la contenant Download PDF

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Publication number
WO2014196768A1
WO2014196768A1 PCT/KR2014/004826 KR2014004826W WO2014196768A1 WO 2014196768 A1 WO2014196768 A1 WO 2014196768A1 KR 2014004826 W KR2014004826 W KR 2014004826W WO 2014196768 A1 WO2014196768 A1 WO 2014196768A1
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WO
WIPO (PCT)
Prior art keywords
polyester resin
biodegradable polyester
acid residue
aliphatic dicarboxylic
mol
Prior art date
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PCT/KR2014/004826
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English (en)
Korean (ko)
Inventor
김예진
강경돈
김수경
김민경
최수연
윤기철
변길석
Original Assignee
삼성정밀화학(주)
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Application filed by 삼성정밀화학(주) filed Critical 삼성정밀화학(주)
Priority to US14/888,268 priority Critical patent/US20160090443A1/en
Priority to EP14807491.7A priority patent/EP3006482A4/fr
Priority to JP2016518260A priority patent/JP2016520706A/ja
Priority to CN201480031251.4A priority patent/CN105263985A/zh
Publication of WO2014196768A1 publication Critical patent/WO2014196768A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • Biodegradable polyester resins and articles comprising the same are disclosed. More specifically, a biodegradable polyester resin prepared by esterification and condensation polymerization of aliphatic dicarboxylic acid and aliphatic diol, and an article having the same are disclosed.
  • Plastics are usefully used in real life because of their high functionality and durability.
  • the conventional plastic has a low decomposition rate due to microorganisms when buried, and it is recognized that problems such as the release of harmful gases during incineration cause the environmental pollution, the development of biodegradable plastics has proceeded.
  • Biodegradable polyester resin refers to a polymer that can be decomposed into water and carbon dioxide or water and methane by microorganisms in nature such as bacteria, algae and mold.
  • Such biodegradable polyester resins have been proposed as a powerful solution to prevent environmental pollution due to landfill or incineration.
  • Biodegradable polyester resins include polyglycolic acid, polyhydroxybutyl acid, polylactic acid, aliphatic polyester, and the like. Polyglycolic acid and polyhydroxybutyl acid obtained by biosynthesis have high manufacturing costs while polylactic acid is a conventional polyolefin resin. Economical price can be secured by forming a price similar to, but it is difficult to apply to products due to the lack of flexibility and tear characteristics.
  • poly (butylene succinate) synthesized by 1,4-butanediol and succinic acid (poly (butylene succinate): PBS) has excellent degradability, melting point similar to polyethylene, and mechanical properties equivalent to those of olefin-based polymers. But it had the disadvantage of low flexibility. In other words, PBS has excellent biodegradability and, despite the possibility that it can be used as a food packaging film to replace conventional plastic, which has been considered as the main cause of environmental pollution, its use was limited due to its lack of flexibility.
  • One embodiment of the present invention provides an excellent biodegradable polyester resin while maintaining biodegradability by including aliphatic dicarboxylic acid residues and aliphatic diol residues.
  • Another embodiment of the present invention provides an article comprising the biodegradable polyester resin.
  • Aliphatic dicarboxylic acid residues including succinic acid residues and adipic acid residues; And aliphatic diol residues including at least one of ethylene glycol residues and butanediol residues.
  • the content of the aliphatic diol residue may be 1 to 2 mol parts based on 1 mol part of the aliphatic dicarboxylic acid residue.
  • the content of the succinic acid residue and the content of the adipic acid residue may be 0.8 to 0.995 moles and 0.005 to 0.2 moles, respectively, relative to 1 mole of the aliphatic dicarboxylic acid residue.
  • the biodegradable polyester resin may further include a terephthalic acid residue.
  • the total content of the adipic acid residue and the terephthalic acid residue may be 0.005 to 0.3 mole parts based on 1 mole portion of the aliphatic dicarboxylic acid residue and the terephthalic acid residue.
  • the content of the succinic acid residue, the content of the adipic acid residue and the content of the terephthalic acid residue are 0.7 to 0.994 mol parts, 0.005 to 0.299 mol parts and 0.001 to 0.295 with respect to 1 mol part of the sum of the aliphatic dicarboxylic acid residues and terephthalic acid residues, respectively. It can be a mole.
  • the biodegradable polyester resin may have a weight average molecular weight of 120,000 ⁇ 350,000.
  • a biodegradable polyester resin excellent in both biodegradability and flexibility can be provided.
  • polyester refers to esterification and polycondensation reactions of one or more difunctional or more polyfunctional carboxylic acids with one or more difunctional or more polyfunctional hydroxyl compounds.
  • the difunctional carboxylic acid is a dicarboxylic acid
  • the difunctional hydroxyl compound is a dihydric alcohol such as glycol or diol.
  • butanediol is a compound in which two hydrogens of butane are substituted with a hydroxy group, and specifically, 1,4-butanediol, 1,3-butanediol and / or 2,3-butanediol means do.
  • crystalstallization means to form a region in which the chains of the resin in the amorphous state or the molten state are partially aligned at any temperature below the melting point and above the glass transition temperature.
  • Biodegradable polyester resins according to an embodiment of the present invention is aliphatic dicarboxylic acid residues comprising succinic acid residues and adipic acid residues; And aliphatic diol residues including at least one of ethylene glycol residues and butanediol residues.
  • the term “residue” means a certain portion or unit derived from the specific compound and included in the result of the chemical reaction when the specific compound participates in the chemical reaction.
  • each of an "aliphatic dicarboxylic acid residue", an “aliphatic diol residue”, and a “terephthalic acid residue” is derived from an aliphatic dicarboxylic acid or a derivative component thereof in a polyester formed by an esterification reaction and a polycondensation reaction. It means a part derived from, an aliphatic diol or a derivative component thereof and a part derived from terephthalic acid or a derivative component thereof.
  • the succinic acid residue may be represented by (-OC-C 2 H 4 -CO-), the adipic acid residue may be represented by (-OC-C 4 H 8 -CO-), ethylene glycol
  • the residue may be represented by (-0-C 2 H 4 -O-)
  • the butanediol residue may be represented by (-0-C 4 H 8 -O-)
  • the terephthalic acid residue is (-OC-C 6 H 4 -CO-).
  • aliphatic dicarboxylic acid derivative means a compound including an ester derivative, an acyl halide derivative, an anhydride derivative and the like of an aliphatic dicarboxylic acid compound.
  • aliphatic diol derivative means a compound containing dimethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, diethylene glycol, triethylene glycol and the like.
  • terephthalic acid derivative means a compound including an ester derivative, an acyl halide derivative, an anhydride derivative and the like of a terephthalic acid compound.
  • the biodegradable polyester resin may be represented by [Formula 1].
  • a is an integer of 1-2500
  • b is an integer of 1-2500
  • m is an integer of 1-1500.
  • R 1 and R 3 may be independently a substituted or unsubstituted C 2 or C 4 alkylene group, one of R 2 and R 4 is a substituted or unsubstituted C 2 alkylene group, the rest is substituted or It may be an unsubstituted C 4 alkylene group.
  • the biodegradable polyesters may be made of poly (ethylene succinate-co- adipate): PESA).
  • PESA poly (ethylene succinate-co- adipate)
  • the biodegradable polyester is polybutylene succinate-adipate (poly (buthylene succinate- co-adipate): PBSA).
  • biodegradable polyester resin further comprises a terephthalic acid residue
  • it may be represented by [Formula 2].
  • a is an integer of 1-2500
  • b is an integer of 1-2500
  • c is an integer of 1-2500
  • m is an integer of 1-1,000.
  • R 1 , R 3 and R 5 may be a substituted or unsubstituted C 2 or C 4 alkylene group independently of each other
  • R 2 , R 4 and R 6 are each a substituted or unsubstituted C 2 alkylene group, It may be a substituted or unsubstituted C 4 alkylene group and a substituted or unsubstituted C 6 phenylene group.
  • the biodegradable polyesters may be polybutylene succinate- Adipate-terephthalate (poly (butylene succinate-co-adipate-co-terephthalate): PBSAT).
  • the biodegradable polyesters are polyethylene succinate-adipates -Terephthalate (poly (ethylene succinate-co-adipate-co-terephthalate): PESAT).
  • the aliphatic dicarboxylic acid and the aliphatic diol when reacting in a stoichiometric ratio, the aliphatic dicarboxylic acid and the aliphatic diol may react at a molar ratio of 1: 1.
  • the amount of the aliphatic diol to the amount of the aliphatic dicarboxylic acid may be 1: 1, but the amount of the aliphatic diol may be excessive compared to the amount of the aliphatic dicarboxylic acid to promote the reaction and increase the yield.
  • the content of the aliphatic diol residue may be 1 to 2 mole parts with respect to 1 mole of the aliphatic dicarboxylic acid residue.
  • the content of the succinic acid residue and the adipic acid residue in the biodegradable polyester resin may be 0.8 to 0.995 moles and 0.005 to 0.2 moles, respectively, relative to 1 mole of the aliphatic dicarboxylic acid residue.
  • the content of the succinic acid residue is within the above range, the crystallization rate and the solidification rate of the biodegradable polyester resin are increased in the pelletization process, so that much time is not consumed in the pelletization, and the biodegradable polyester having high flexibility and improved flexibility Resin can be obtained.
  • a biodegradable polyester resin having high molecular weight and high strength and improved flexibility may be obtained.
  • the biodegradable polyester resin may further include a terephthalic acid residue.
  • the terephthalic acid residue is not included in the aliphatic dicarboxylic acid residue, but may be derived from terephthalic acid or dimethyl terephthalate, which may react with diol to cause an esterification reaction.
  • aromatic carboxylic acid residues in the resin serve to increase the strength of the resin by providing the resin with high crystallinity.
  • the biodegradable polyester resin further includes a terephthalic acid residue, the crystallization rate and the solidification rate of the resin increase in the pelletization process, which is advantageous for pelletization, and a biodegradable polyester resin having high flexibility and improved flexibility can be obtained. have.
  • the total content of the adipic acid residue and the terephthalic acid residue in the biodegradable polyester resin may be 0.005 to 0.3 mole parts based on 1 mole part of the sum of the terephthalic acid residue and the aliphatic dicarboxylic acid residue.
  • the crystallization rate and the solidification rate of the biodegradable polyester resin in the pelletizing process is increased, so much time for pelletization It is possible to obtain a biodegradable polyester resin that is not consumed and has high strength and improved flexibility.
  • the content of the succinic acid residues, the content of the adipic acid residues and the content of the terephthalic acid residues are 0.7 to 0.994 mol parts, 0.005 to 0.299 mol parts and 0.001 to 0.295 with respect to 1 mol part of the sum of the aliphatic dicarboxylic acid residues and the terephthalic acid residues, respectively. It may be mole.
  • the biodegradable polyester resin may have a weight average molecular weight of 120,000 ⁇ 350,000.
  • the biodegradable polyester resin may have a weight average molecular weight of 140,000 to 350,000.
  • an article comprising the biodegradable polyester resin comprising the biodegradable polyester resin.
  • Articles comprising the biodegradable polyester resin may include, for example, medical articles such as sutures, mouthpieces, etc., which require flexibility; One-time household items such as envelopes, shopping bags, gloves, tablecloths, and the like; Fishing nets / fishing articles such as fishing nets, fishing lines, green nets and the like; Building materials such as drain boards; And agricultural mulching films.
  • the biodegradable polyester resin as described above can be produced by the following method. That is, the biodegradable polyester resin is an esterification reaction and a polycondensation reaction of an aliphatic dicarboxylic acid or a derivative thereof corresponding to the aliphatic dicarboxylic acid residue and an aliphatic diol or a derivative thereof corresponding to the aliphatic diol residue.
  • the biodegradable polyester resin is an esterification reaction and a polycondensation reaction of an aliphatic dicarboxylic acid or a derivative thereof corresponding to the aliphatic dicarboxylic acid residue and an aliphatic diol or a derivative thereof corresponding to the aliphatic diol residue.
  • aliphatic dicarboxylic acid or derivative thereof including succinic acid and adipic acid
  • an aliphatic diol containing at least any one of ethylene glycol and butanediol or a derivative thereof is esterified to obtain an oligomer having an ester bond
  • a biodegradable polyester resin can be produced by condensation polymerization of the oligomer.
  • the amount of aliphatic diol or derivative thereof used in the esterification reaction may be 1.0 to 2.0 mole parts based on 1 mole part of the aliphatic dicarboxylic acid or derivative thereof.
  • the amount of the aliphatic diol or its derivative is within the above range, not only the aliphatic dicarboxylic acid or its derivative is completely reacted, but also the ester bond is destroyed by acidolysis reaction due to the remaining dicarboxylic acid. There is no fear of depolymerization, and there is no problem of cost increase due to the excessive use of the aliphatic diol.
  • the amount of succinic acid and adipic acid used in the esterification reaction may be 0.8 to 0.995 moles and 0.005 to 0.2 moles, respectively, based on 1 mole of the aliphatic dicarboxylic acid.
  • aliphatic dicarboxylic acids or derivatives thereof including succinic acid and adipic acid
  • Aliphatic diols or derivatives thereof including at least one of ethylene glycol and butanediol
  • an esterification reaction of terephthalic acid or a derivative thereof to obtain an oligomer having an ester bond and a biodegradable polyester resin can be produced by condensation polymerization of the oligomer thus obtained.
  • the sum of the amount of the adipic acid and the amount of the terephthalic acid or the derivative thereof may be 0.005 to 0.3 mole parts based on 1 mole of the total amount of the terephthalic acid or its derivatives and the aliphatic dicarboxylic acid or its derivatives. have.
  • the amount of the succinic acid, the amount of the adipic acid, and the amount of the terephthalic acid or its derivatives is 0.7 to 0.994 moles, respectively, based on the total amount of the amount of the terephthalic acid or its derivatives and the amount of the aliphatic dicarboxylic acid or its derivatives used. , 0.005 to 0.299 mole parts and 0.001 to 0.295 mole parts.
  • Such esterification reaction may proceed for 80 to 450 minutes at 140 ⁇ 200 °C.
  • the esterification reaction may be performed at 140 to 190 ° C. for 80 to 240 minutes.
  • the esterification reaction may be performed at 140 to 200 ° C. It can run for 150-450 minutes.
  • the end point of the esterification reaction can be determined by measuring the amount of alcohol or water by-produced in this reaction. For example, when 0.95 mol and 0.05 mol of succinic acid and adipic acid are used as aliphatic dicarboxylic acid, and 1.3 mol of ethylene glycol is used as aliphatic diol, all amounts of succinic acid and adipic acid used are ethylene. Assuming that it reacts with glycol, the esterification reaction can be terminated if at least 90% of the 2 mol of water to be by-products, ie, at least 1.8 mol, are by-produced.
  • succinic acid, adipic acid, and dimethyl terephthalate are used as dicarboxylic acids, respectively, 0.9 mol, 0.05 mol, and 0.05 mol, and 1.3 mol of butanediol is used as aliphatic diol
  • succinic acid, adipic is used.
  • the esterification reaction is terminated when at least 90% of 1.9 mol of water and 0.1 mol of methanol to be by-produced, i.e., 1.71 mol of water and 0.09 mol of methanol, are produced by-product. can do.
  • by-product alcohol, water and / or unreacted diol compound may be discharged out of the reaction system by evaporation or distillation.
  • the esterification reaction may be performed in the presence of a catalyst, a branching agent, a heat stabilizer and / or a color regulator.
  • the catalyst includes magnesium acetate, stannous acetate, tetra-n-butyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, N, N-dimethylaminopyridine, N-methylimidazole or combinations thereof can do.
  • the catalyst is usually added simultaneously with the monomer when the monomer is added.
  • the amount of the catalyst used may be, for example, 0.00001 to 0.2 mole parts based on 1 mole part of the aliphatic dicarboxylic acid.
  • the reaction time can be shortened, a desired degree of polymerization can be obtained, and a biodegradable polyester resin having high tensile / tear strength and good color can be obtained.
  • the heat stabilizer may be an organic or inorganic phosphorus compound.
  • the organic or inorganic phosphorus compound may be, for example, phosphoric acid and its organic esters, phosphorous acid and its organic esters.
  • the thermal stabilizer is a commercially available material and may be phosphoric acid, alkyl or aryl phosphates.
  • the heat stabilizer may be triphenyl phosphate.
  • the amount of the thermal stabilizer used in the case of using the catalyst and the thermal stabilizer together may be, for example, 0.00001 to 0.2 mol part with respect to 1 mol part of the aliphatic dicarboxylic acid. If the amount of the heat stabilizer is within the above range, deterioration and discoloration of the biodegradable polyester resin can be prevented.
  • the branching agent is used for the purpose of controlling the biodegradability and physical properties of the polyester resin.
  • branching agents compounds having three or more ester or amide-formable groups selected from carboxyl groups, hydroxyl groups and amine groups can be used.
  • trimellitic acid, citric acid, maleic acid, glycerol, monosaccharides, disaccharides, dextrins, or reduced sugars may be used.
  • the amount of the branching agent may be 0.00001 to 0.2 mol based on 1 mol part of the aliphatic dicarboxylic acid.
  • amount of the branching agent used is within the above range, a high molecular weight biodegradable polyester resin having excellent tensile strength and tear strength can be obtained.
  • the esterification reaction may be carried out at normal pressure.
  • normal pressure means a pressure in the range of 760 ⁇ 10 torr.
  • the color control agent is an additive used to adjust the chromaticity of the biodegradable polyester resin.
  • Cobalt acetate may be used as the color adjusting agent.
  • Such color regulators may be used in the esterification step together with aliphatic diols and aliphatic dicarboxylic acids, or may be used in the condensation polymerization step described below.
  • the amount of the color adjusting agent may be 0.00001 to 0.2 mol based on 1 mol part of the aliphatic dicarboxylic acid.
  • the product of the above esterification reaction may be further condensation polymerization reaction for high molecular weight.
  • the polycondensation reaction may be performed at 220 to 290 ° C. for 120 to 360 minutes.
  • the condensation polymerization may be performed at 240 to 290 ° C. for 240 to 360 minutes, and when the butanediol is used as the aliphatic diol, the condensation polymerization is at 220 to 250 ° C. It can run for 120-280 minutes.
  • the polycondensation reaction may proceed at a pressure of 1 torr or less.
  • a high molecular weight biodegradable polyester resin can be obtained, removing an unreacted raw material (unreacted monomer), a low molecular oligomer, and the by-product water.
  • ethylene glycol EG
  • SA succinic acid
  • AA adipic acid
  • TBT tetra-n-butyl titanate
  • MA malic acid
  • TPP triphenyl phosphate
  • CA cobalt acetate
  • PBSA was synthesized using the same method as the synthesis method of PESA in Examples 1 to 3, except that 1,4 butanediol (BDO) was used instead of ethylene glycol (EG).
  • BDO 1,4 butanediol
  • EG ethylene glycol
  • Example 1 124.14 (2.0) - 112.19 (0.95) 7.31 (0.05) 0.4 (2.983) 1.0 (3.065) 0.15 (0.440) 1.0 (0.201)
  • Example 2 124.14 (2.0) - 117.50 (0.995) 0.73 (0.005) 0.4 (2.983) 1.0 (3.065) 0.15 (0.440) 1.0 (0.201)
  • Example 3 124.14 (2.0) - 106.28 (0.9) 14.61 (0.1) 0.4 (2.983) 1.0 (3.065) 0.15 (0.440) 1.0 (0.201)
  • Example 4 180.24 (2.0) 94.47 (0.8) 19.23 (0.2) 0.3 (2.237) 0.1 (0.307) 0.25 (0.735) 0.4 (0.080)
  • Example 5 Example 5
  • PBSAT was synthesized using the same method as the synthesis method in Examples 7-8, except that cobalt acetate (CA) was not used as the color regulator.
  • CA cobalt acetate
  • PESAT was synthesized using the same method as the synthesis method of Examples 7 to 8 except that ethylene glycol (EG) was used instead of 1,4-butanediol (BDO).
  • EG ethylene glycol
  • BDO 1,4-butanediol
  • polybutylene succinate poly (butylene succinate): PBS
  • S-EnPol 4560M polybutylene succinate (poly (butylene succinate): PBS) from S-EnPol was used.
  • Weight average molecular weight (Mw), melt flow index (MFI), flexural strength, biodegradability and processability of the biodegradable polyester synthesized in Examples 1 to 11 and PBS resin of Comparative Example 1 was measured in the following manner, and the results are shown in Table 5 below.
  • the solution obtained by diluting the polyester resins of the Examples and Comparative Examples in 1 wt% concentration in chloroform was analyzed by gel permeation chromatography (GPC) to determine the weight average molecular weight.
  • GPC gel permeation chromatography
  • melt flow index measured the amount of g flowing out for 10 minutes under a load of 2.16 kg at 190 ° C., according to ASTM D1238.
  • Flexural strength was modified by ASTM D790 method to produce an injection specimen of length / width / thickness of 8 cm / 1.2 cm / 0.4 cm, and then placed the specimen on a U-shaped support, and then using 10 kN load using Instron. A force was applied to the center of the specimen between the supports to measure the maximum value of the force until the displacement in the vertical direction (ie, the direction parallel to the thickness direction of the specimen) was 10 mm. At this time, the distance between the two points of the support in contact with the specimen was 70mm, measured three times and recorded the average value as the bending strength.
  • the smaller the flexural strength the better the flexibility.
  • Biodegradability evaluation was performed according to KS M 3100-1, a method for measuring aerobic biodegradability of plastics in composting conditions.
  • the cumulative biodegradation value that proceeded for a total of 45 days was calculated by Equation 1 below, and is shown in Table 5 below.
  • Processability was evaluated by judging the time required for the resin to crystallize when the polymerized final resin was left at room temperature (25 ° C.).
  • the time taken for crystallization means the time taken for the transparent resin (melted state) to turn white (crystal state) when visually observed. The results are shown in Table 5.
  • the biodegradable polyester resin of Example 1-11 has a high weight average molecular weight (172,000 or more) and improved flexibility (20 Mpa or less) compared to the biodegradable polyester resin of Comparative Example 1 It can be seen that the castle is maintained (more than 60%).
  • the biodegradable polyester resin of Example 7-11 has a higher tensile strength than the polyester resin of Examples 1-6, because it further has high crystallinity by further including a terephthalic acid residue.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Polyesters Or Polycarbonates (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

Cette invention concerne une résine polyester biodégradable et un article la contenant. La résine polyester biodégradable décrite contient un résidu acide dicarboxylique aliphatique contenant un résidu acide succinique et un résidu acide adipique, et un résidu diol aliphatique contenant au moins un résidu éthylène glycol et/ou un résidu butane diol, afin d'améliorer la biodégradabilité et la flexibilité.
PCT/KR2014/004826 2013-06-05 2014-05-30 Résine polyester biodégradable et article la contenant WO2014196768A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US14/888,268 US20160090443A1 (en) 2013-06-05 2014-05-30 Biodegradable polyester resin and article containing the same
EP14807491.7A EP3006482A4 (fr) 2013-06-05 2014-05-30 Résine polyester biodégradable et article la contenant
JP2016518260A JP2016520706A (ja) 2013-06-05 2014-05-30 生分解性ポリエステル樹脂、及びそれを含む物品
CN201480031251.4A CN105263985A (zh) 2013-06-05 2014-05-30 可生物降解的聚酯树脂以及含有该树脂的物品

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KR10-2013-0064966 2013-06-05
KR1020130064966A KR20140143045A (ko) 2013-06-05 2013-06-05 생분해성 폴리에스테르 수지 및 이를 포함하는 물품

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EP (1) EP3006482A4 (fr)
JP (1) JP2016520706A (fr)
KR (1) KR20140143045A (fr)
CN (1) CN105263985A (fr)
TW (1) TW201504332A (fr)
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KR102196219B1 (ko) * 2020-04-09 2020-12-29 엔비코 주식회사 잉크용 생분해성 폴리에스터수지 및 그 제조방법
CN113563728A (zh) * 2020-04-29 2021-10-29 昊博(山东)新材料科技有限公司 一种可生物降解的排水板及其制备工艺

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TW201504332A (zh) 2015-02-01
EP3006482A4 (fr) 2016-10-12
EP3006482A1 (fr) 2016-04-13
JP2016520706A (ja) 2016-07-14
US20160090443A1 (en) 2016-03-31
KR20140143045A (ko) 2014-12-15

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